JPH07508778A - Additives and fuel compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Additives and fuel compositions The invention relates to crude oil, lubricating oil or fuel oil, such as distilled petroleum fuel, e.g. To improve the low temperature flow properties of middle distillate fuel oils boiling within the range of ℃ to 500℃ Regarding the use of additives.

When oils and fuel oils are exposed to low ambient temperatures, the wax separates from the fuel and the oil may impair the flow properties of the product. For example, middle distillate fuels precipitate at low temperatures and Produces large crystals of wax that tend to clog small openings in filters Contains wax. This problem is particularly acute when the fuel is diesel fuel. be. After all, the nominal diameter of a diesel engine's fuel filter is typically This is because the diameter is approximately 5 to 50 microns. To solve the above problem Additives are known in the art and are referred to as flow modifiers.

When such additives are blended with waxy mineral oil, the wax therein changes the shape and size of crystals and reduces the cohesive force between crystals and between wax and oil wax by causing the oil to remain fluid at a lower temperature than in the absence of additives. It can act as a cous crystal modifier.

European Patent Application No. 0261957 improves the cold flow properties of distillate fuels describes the use of additives for ethylene-vinyl acetate copolymers or Additives containing mixtures of ethylene-vinyl acetate copolymers (added in the specification) (referred to as agent A) to form a half-amide/half-amine salt. Addition containing the reaction product of 1 mole of phthalic anhydride and 2 moles of dihydrogenated beef tallow amine (referred to in the specification as Additive C). European Patent Application No. 026 A particular example of Additive A used in conjunction with Additive C in the '1957 specification is the additive A1, which is an I:3 (W/iv) mixture of two copolymers, one of which is The other is A2 defined below, and the other is A3 defined below. In this way, A1 The average vinyl acetate content is 32.75% by weight, or 13.7% by mole.

Additive A2, which consists of ethylene and approximately 17% by weight vinyl acetate, has a gas phase osmotic pressure about 3000 Mn, i.e. 6.25 mol% vinyl acetate, as determined by the VPO method. is a copolymer with nyl; Additive A3, which consists of ethylene and approximately 38% by weight vinyl acetate, is of about 1800 \1n, or 16.6 mole % vinyl acetate, as measured by is a polymer: and Additive A4, which is a 50:50 fi combination of additives A2 and A3 defined above. Therefore, the average vinyl acetate content of A4 is 27.5% by weight, i.e. 11 mol %.

Mn in this specification is the number average molecular weight, and unless otherwise specified, Mn is the number average molecular weight. as determined by gel permeation chromatography (GPC) against standard materials. It is.

The problem with the use of the above additives is that Additive A affects the cold flow properties of the distilled fuel. It has good performance on its own to improve, but when used in combination with Additive C The problem is that they do not necessarily exhibit good low-temperature flow properties when used. The present invention By using an additive with mol% comonomer, e.g. vinyl acetate Eliminating that problem, the use of additives with such specific mol% As illustrated in the examples, the comparison additives showed significant improvement in the cold flow properties of middle distilled fuel oils. yields unexpected and surprising benefits over use.

Thus, in a first aspect, the invention comprises ethylene and an unsaturated monomer of the general formula - (In the formula, R6 is hydrogen or methyl, R5 is 10OCR" group (In the formula, R1 is Hydrogen formate or Cl-C21, more usually C1-C1□, preferably C, -C, is a straight-chain or branched alkyl group), or R' is a -COOR' group (of the formula where R' is as defined above but is not hydrogen), and R7 is hydrogen or the above-mentioned -COOR' group, and (i) a copolymer with more than -n If present, the arithmetic mean content of said unsaturated monomers in the copolymer is 11 mol. % or (ii) if one copolymer is present, in the copolymer The content of said unsaturated monomers ranges from 6.5 to 11 mol %, preferably 10 mol %. %) of one or more oil-soluble copolymers.

In a second aspect, the invention relates to crude oils, lubricating oils or fuel oils, such as middle distillate Proposes the use of the additive of the first aspect of the invention for improving the cold flow properties of fuel oil. provide

In a third aspect, the invention provides long ratio crude oils, lubricating oils or fuel oils, such as Composition comprising a mixture of middle distillate fuel oil and a small proportion of the additive of the first aspect of the invention I will provide a.

In a fourth aspect, the invention provides a crude oil, a lubricating oil or a fuel oil, e.g. Additive As the unsaturated monomer, C1-C, monocarboxylic acid, for example, C8-C, monocarboxylic acid, Examples include alcohol esters of nocarboxylic acids. An example of a monomer is vinyl acetate. vinyl, vinyl propionate, vinyl butyrate or vinyl isobutyrate, vinyl hexanoate vinyl acetate and vinyl propionate are preferred. Yes.

The copolymer has a molecular weight of 1,000 to 10,000, preferably More preferably, it has a number average molecular weight of 1.000 to 5.000. as desired In addition, the copolymer may be derived from additional comonomers, e.g. Terpolymers or tetrapolymers or e.g. In the case of iso-olefins such as sobutylene or di-isobutylene, further It may also be a multicomponent copolymer.

If more than one copolymer is present, the arithmetic mean of the content of said unsaturated monomers is preferably 5 to 10 mol%, more preferably 6 to 10 mol%, for example 7 or is 8 to lθ mol%.

If one copolymer is present, the content of said unsaturated monomers is preferably from 7 to 10 mol%, more preferably 8 to 10 mol%, most preferably 8 to 9 mol%. Ru.

Such copolymers are produced by copolymerizing ethylene with the unsaturated monomers mentioned above. Can be manufactured. Also, they yield different ethylenically unsaturated ester copolymers transesterification or hydrolysis of ethylenically unsaturated ester copolymers for It can be produced by re-esterification. For example, ethylene vinyl hexanoate copolymer and ethylene vinyl octoate copolymers, such as ethylene vinyl acetate copolymers. It can be produced in this way from polymers.

oil The oil may be crude oil, i.e. oil obtained directly from drilling, prior to refining, and may be The compounds are suitable for use as flow modifiers or dewaxing aids therein.

The oil may be a lubricating oil, which may be an animal oil, a fruit oil, a vegetable oil or a mineral oil, e.g. , naphtha or spindle oil to 5AE30, 40 or 5o lubricating oil gray It may also be a petroleum distillate, castor oil, fish oil or oxidized mineral oil ranging from 100 to 100 ml. this Such oils may contain additives depending on their intended use. An example is the viscosity index modified Examples are additives and zinc dialkyl-dithiophosphate anti-wear additives. Book The additives of the invention can be used in lubricating oils as flow modifiers, pour point depressants or dewaxing aids. may be suitable for use.

The oil may be a fuel oil, for example a petroleum-based fuel oil, preferably a middle distillate fuel oil. . Such distillate fuel oils generally have a temperature of about 10°C to about 50°C, e.g. Boils within the range of 400°C to 400°C. Fuel oil can be atmospheric distillate or vacuum distillate, or cracked gas oils or straight runs and pyrolyzed and/or catalytically cracked distillates. It may be a blend in any proportion. The most common petroleum distillate fuel is kerosene. , jet fuel, diesel fuel, heating oil and heavy fuel oil. heating o The oil may be a straight run at atmospheric pressure, or it may be present in small amounts, e.g. up to 35% by weight. may contain vacuum gas oil or cracked gas oil or both. Up The cold flow problems described above are most commonly found in diesel fuel and heating oil. . The present invention also relates to vegetable fuel oils or other vegetable fuel oils, such as rapeseed oil ( For example, as its methyl ester).

The concentration of the additive in the oil may be, for example, 10 to 2.00 on a weight basis per weight of fuel. 0 ppm, for example 50, preferably 25 to 500 ppm, more preferably 1 00 to 200 ppm of additives (active ingredients). Additive concentrates are It may also contain auxiliary additives as described below.

The additive contains at least 11,000 ppm on a weight basis per weight of oil at ambient temperature. It should be soluble in oil to some degree. However, at least some of the additives can precipitate out of solution near the cloud point of the oil to modify the wax crystals that form. .

The ratio of additive to co-additive, e.g. 0:1-1:20, such as 10:1-1:10, preferably 5:1-1:5. All ratios are weight:weight.

Auxiliary additive The additive of the present invention improves the cold flow properties of crude oil, lubricating oil or fuel oil, as described above. It may be used in combination with one or more oil-soluble co-additives for modification. This way Examples of co-additives include polar nitrogen compounds, comb polymers, polyoxyalkylene may be selected from carbon compounds, hydrocarbon polymers, and sulfur carboxy compounds. this Such auxiliary additives will be described in more detail.

(i) Polar nitrogen compound Oil-soluble polar nitrogen compounds may be ionic or dipolar, for example: It may contain one or more of compounds (A) to (B).

(A) at least 1 molar ratio of a hydrocarbyl-substituted amine to 1 to 4 carboxylic acids; By reacting with 1 molar ratio of hydrocarbylic acid or its acid anhydride having groups A total of 30 to 300 amine salts and/or amides, preferably 50 Esters/amides containing up to 150 carbon atoms may be used. These nitrogen compounds A product is described in US Pat. No. 4,211,534. Suitable amines are commonly Usually long chain C,2-C,. -class, secondary, tertiary or quaternary amines or mixtures thereof. compound, but the resulting nitrogen compound is oil-soluble and therefore usually has a total content of about 30 to Short chain amines may be used provided they contain 300 carbon atoms. Nitrogen compound The substance has at least one straight chain C*-C+. , preferably Cl4-Cf4 alkylcetate It is preferable to include a component.

Suitable amines include -class, secondary, tertiary or quaternary, with secondary That's good, desirable. Only tertiary and quaternary amines can form amine salts. a Examples of minerals include tetrazodinogenine, cocoamine, and hydrogenated tallowamine. It will be done. Examples of secondary amines include dioctadecylamine and methyl-behenylamine. One example is Min. Also, amine mixtures, e.g. amines derived from natural substances. Preference is given to mixtures of Preferred amines have the formula HNR'R'', where R1 and R8 is hydrogenated beef tallow containing approximately 4% C++, 3t% Cps, and 59% Cl. It is a secondary hydrogenated beef tallow amine with an alkyl group derived from

Examples of carboxylic acids and their anhydrides suitable for preparing nitrogen compounds include: Cyclohexane 1, 2 dicarboxylic acids, cyclohexene 1. 2 dicarboxylic acid, Clopentane 1. 2 dicarboxylic acid and naphthalene dicarboxylic acid, and dial Contains Kirspirobislactone! , 4-dicarboxylic acid. Generally, this These acids have about 5 to 13 carbon atoms in their cyclic portion. beneficial to the invention Preferred acids are benzenedicarboxylic acids, such as phthalic acid, isophthalic acid, and It is phthalic acid. Particularly preferred is phthalic acid or its acid anhydride. particularly preferred The compound is prepared by reacting 1 molar ratio of phthalic anhydride with 2 molar ratio of dihydrogenated beef tallow amine. This is an amide-amine salt produced by Other preferred compounds include It is a diamide produced by dehydrating the amide-amine salt of

Other examples are long chain alkyl or alkylene substituted dicarboxylic acid derivatives, e.g. , amine salts of monoamides of substituted succinic acids, examples of which are known in the art. , for example, in US Pat. No. 4,147,520. suitable amines can be an amine as described above.

Other examples include condensation as described in European Patent Application No. 327.423. It is a thing.

(B) A chemical compound containing a ring system, in which the ring system has the following general formula (1) % formula % ( 1) A compound having at least two substituents of aliphatic hydrides which may be interrupted by teloatoms and which are straight or branched; is a locarbyl group, and R1 and R1 are the same or different, each independently 9 to 40 carbon atoms, optionally interrupted by one or more heteroatoms A hydrocarbyl group containing elementary atoms, and these substituents may be the same or different. and the compound may be in the form of its salt if necessary) A preferably has 1 to 20 carbon atoms and is a methylene group or a polymethyl Preferably it is a ren group.

"Hydrocarbyl" herein means an organic moiety containing hydrogen and carbon; Unless otherwise specified, it refers to aliphatic including cycloaliphatic; aromatic; or any of these. Any combination may be used. It can be substituted or unsubstituted alkyl, aryl or aralkyl, and may contain unsaturation if necessary.

Examples when it is substituted are oxy-hydrocarbyl, halogeno-hydro carbyl and hydroxy-hydrocarbyl.

As ring systems, monocyclic assemblies, heterocyclic assemblies, or fused polycyclic acyclic assemblies assembly, or two or more such annular assemblies joined together and the annular assemblies may be the same or different. One example is the eel type. If two or more such annular assemblies exist, The substituents of general formula (1) are of the same assembly or of different assemblies, preferably may exist in the same assembly.

Preferably the or each cyclic assembly is aromatic. , a benzene ring is more preferable. The ring system has a substituent in the ortho or meta position. A single benzene ring is most preferred; The benzene ring may be further substituted if necessary.

Preferably, the ring atoms in one or more cyclic assemblies are carbon atoms, but e.g. For example, it may contain one or more ring N, S or O atoms, in which case or in these cases the compound is a heterocyclic compound.

Examples of such polycyclic assemblies include (a) fused benzene structures, e.g. naphthalene, anthracene, phenanthrene, and pyrene; (b) fused ring structures in which none or some of the rings are benzene, e.g. , azulene, indene, hydroindene, fluorene, and diphenylene; (C ) “terminally” attached rings, e.g. diphenyl; (d) heterocyclic compounds, e.g. , quinoline, indole, 2:3 dihydroindole, benzofuran, kumari isocoumarin, benzothiophene, carbazole and thiodiphenylamine ; (e) non-aromatic or partially saturated ring systems, such as decalin (i.e. decahydro naphthalene), α-pinene, caldinene, and polynylene; and (f) three-dimensional structure, e.g., norbornene, bicyclohebutane (i.e., norbornane), Examples include clooctane and bicyclooctene.

Each hydrocarbyl group constituting R1 and R'' (Formula I) is, for example, an alkyl or alkylene group or mono-alkoxyalkyl group or poly-alkyl group or It may also be a lucoxyalkyl group. Each hydrocarbyl group is a straight chain alkyl group It is preferable that The number of carbon atoms in each hydrocarbyl group is from 16 to 40 The number is preferably 16 to 24, and more preferably 16 to 24.

In addition, the science type is substituted with only two substituents of general formula (1), and A is methyl Preferably it is a ren group.

Examples of salts of chemical compounds are acetate and hydrochloride.

These compounds are prepared by reacting a secondary amine with the appropriate acid chloride. may be conveniently prepared by reducing the (C) Special examples of condensates of long-chain-class or secondary amines and carboxylic acid-containing polymers British Patent No. 2.121.807, French Patent No. 2.592.387 and polymers as described in German Patent No. 3.941.561; and and telemeric acid and acetic acid as described in U.S. Pat. No. 4,639,256. esters of lukanolamine; as well as those described in U.S. Pat. No. 4,631,071; Amines, epoxides and monocarbons containing branched carboxylic acid esters such as Mention may be made of reaction products of rubonic acid polyesters.

(ii) Comb polymers (<C-shaped polymers) Such polymers are It is a polymer in which the building group is pendant from the polymer main chain, and is called a “comb”. -like polymers: structure and properties J, Po1y, Sci, MaCrOmOIeCular Revs, 8 ．． pp. 117-253 (1974j) explained.

Advantageously, the comb polymer has a molecular weight of at least 25, preferably at least 40, even more. preferably at least 50 mol% of the units are at least 6, preferably at least Both are homopolymers or copolymers with side chains containing 10 atoms.

Examples of preferred comb polymers include comb polymers of the general formula.

(In the formula, D=R", C00R", 0COR", R"C0OR", or 0R11, E=H SCH,,D, or RI2, G=H or D J=H, R", R"COOR person or aryl group or heterocyclic group, K=H, C 00R12,0CORI2,OR", or C00H1L=H,R",C0OR '2.0COR'', C00H1 or aryl, R''≧01°hydrocarbyl, R”≧CI hydrocarbyl, and m and n represent the molar ratio, m is in the range of 1.0 to 0.4, and n is in the range of 0 to 0.6. range. Rl represents a hydrocarbyl group having 10 to 30 carbon atoms It is advantageous for Rl2 to be a hydrocarbon having 1 to 30 carbon atoms. (advantageously represents a rubyl group) Comb polymers may be derived from other monomers as desired or necessary. It may also include units. Contains two or more different comb copolymers are within the scope of this invention.

These comb polymers contain maleic anhydride or fumaric acid and other ethylene unsaturated monomers, such as alpha-olefins or unsaturated esters, such as vinegar It may also be a copolymer with vinyl acid. Equimolar amounts of comonomers are used. is preferred, but not essential, and molar ratios in the range of 2:1 to 1:2 are preferred.

For example, examples of olefins that can be copolymerized with maleic anhydride include l-decene, l- -dodecene, l-tetradecene, l-hexadecene, and l-octadecene. can be lost.

The copolymer may be esterified by any suitable technique and may also be anhydrous. Although it is preferred that the leic acid or fumaric acid is at least 50% esterified, Not required. Examples of alcohols that can be used include n-decane-1-ol, n -dodecane-1-ol, n-tetradecan-■-ol, n-hexadecane- 1-ol, and n-octadecane-1-ol. Also, alcohol The chain may contain up to one methyl branch per chain, e.g. Decane-1-ol and 2-methyltridecane-1-ol may also be used. Al Cole may be a mixture of straight chain alcohols and single methyl branched alcohols . It is preferable to use pure alcohol rather than commercial alcohol mixtures but when a mixture is used, part 2 represents the average number of carbon atoms in the alkyl group.

If an alcohol containing a branch in the 1st or 2nd position is used, RI'' is the alcohol represents the linear backbone segment of the core.

These comb polymers are especially fumarate or itaconate polymers. polymers and copolymers, e.g. European Patent Application No. 153176, European Patent Application No. 15317 Described in No. 7 and No. 225688, and the specification of Wo 91/16407 It may be something like that.

A particularly preferred fumarate comb polymer is a combination of an alkyl fumarate and vinyl acetate. copolymers (in which case the alkyl groups have 12 to 20 carbon atoms), More specifically, for example, a mixture of equimolar amounts of fumaric acid and vinyl acetate may be solution copolymerized. , the resulting copolymers are converted into alcohols or alcohols (these are linear alcohols). a polymer (preferably) made by reacting it with a mixture of (preferably In this case, the alkyl group has 14 carbon atoms, or the alkyl group CD/C1, which is a mixture of alkyl groups). If the mixture is used , it is a mixture of l:l linear cps alcohol and linear cps alcohol on a weight basis It is advantageous to be a thing. Furthermore, C11 ester and mixed C+ +/C+ *E Mixtures of stells may advantageously be used. In such a mixture, Cu vs. C+ +/C+s ratio ranges from 1:1 to 4:1, preferably from 2:1 to 7:2 on a weight basis. Advantageously, the ratio is about 3:1, most preferably about 3:1.

Other suitable comb polymers include polymers and copolymers of alpha-olefins. and esterified copolymers of styrene and maleic anhydride, and styrene and fumaric anhydride. It is an esterified copolymer of acid. A mixture of two or more comb polymers and, as noted above, such use may be advantageous. .

(iii) Examples of polyoxyalkylene compounds include polyoxyalkylene esters, Ethers, esters/ethers and mixtures thereof, especially at least one, preferably Preferably at least two C1° to C3° linear saturated alkyl groups and up to 5,000 and preferably a polyoxyalkylene glycol with a molecular weight of 200 to s, ooo. containing 1 to 4 alkyl groups in the polyoxyalkylene glycol. Contains carbon atoms. These substances are described in European Patent Publication No. 0061895A2 form the subject of the issue. Other such additives are described in U.S. Pat. No. 4,491,455. It is stated in the specification.

Preferred esters, ethers or esters/ethers that can be used are is the formula %formula% It can be expressed as

(wherein R and R20 are the same or different, (a) n-alkyl (b) n-alkyl-C- (c) n-alkyl-0-C(CHl), -(d) n-alkyl-0-C- (CH,), -C-, and n is, for example, 1 to 30, and the alkali The kill group is linear and saturated and contains 10 to 30 carbon atoms, and A is a group Recall's polyalkylene segment (the alkylene group has 1 to 4 carbon atoms) ), for example, a polyoxymethylene moiety, a polyoxyethylene moiety or Represents a polyoxytrimethylene moiety (which is linear in nature) and represents a lower alkyl degree of branching due to side chains (e.g., polyoxypropylene glycol) It is preferred that the glycol is substantially linear. A is also Suitable glycols (which may contain nitrogen) generally contain about 100-s, ooo , preferably a substantially linear polyethylene having a molecular weight of about 200 to 2.000. glycol (PBG) and polypropylene glycol (PPG). S Glycols are preferred and fatty acids containing 10 to 30 carbon atoms react with glycols. It is useful for producing ester additives in response to c++-c2+ fatty acids, especially Preferably, behenic acid is used. In addition, ester is a polyethoxylated resin. Can be prepared by esterifying fatty acids or polyethoxylated alcohols .

Polyoxyalkylene diesters, diethers, ethers/esters and these mixtures of are suitable as additives, diesters with small amounts of monoethers and mono In cases where esters (these are often produced during the manufacturing process) may also be present Preferred for use in narrow boiling distillates. Large amounts of dialkyl compounds are present This is important for additive performance. In particular, polyethylene glycol, polypropylene Steary of glycol or polyethylene/polypropylene glycol mixture Preference is given to diesters of behenic acid or behenic acid.

Examples of other compounds in this general category include JP-A-2-51477 and No. 3-34790 and European Patent Application No. 117.1 Esterification alkoxylation described in No. 08 and No. 326, 356 It is an amine.

(iv) Hydrocarbon polymer An example is the general formula below (In the formula, T=H or alkyl U=H, T or aryl v-1.0 to 0.0 (molar ratio) w=o, O-1,0 (molar ratio)) It is a substance represented by

These polymers may be made directly from ethylenically unsaturated monomers or hydrogenation of polymers made from monomers such as isoprene, butadiene, etc. It may also be produced indirectly by

Preferred hydrocarbon polymers have a number average molecular weight of at least 30.000 , a copolymer of ethylene and at least one α-olefin. α-olef Preferably, the fins have at most 20 carbon atoms. Orefy like this Examples include propylene, -butene, isobutyne, n-octene-1, They are ten-1, n-decene-■, and n-dodecene-1. Also, the copolymer , small amounts, e.g. up to 10% by weight, of other copolymerizable monomers, e.g. It may contain olefins other than olefins and non-conjugated dienes. Preferred co The polymer is an ethylene-propylene copolymer. Two or more different species of this kind It is within the scope of this invention to include ethylene-α-olefin copolymers.

The number average molecular weight of the ethylene-α-olefin copolymer is Measured by gel permeation chromatography (GPC) against a tyrene standard. , at least 30,000, advantageously at least 60,000. preferably less The minimum is 80.000. Functionally, there is no upper limit, but the difficulty of mixing is about 150.0 Due to increased viscosity at molecular weights above 0.00, the preferred molecular weight range is 60.00. 000 to so, ooo to 120.000.

Advantageously, the copolymer has a molar ethylene content of 50 to 85%. Even more advantageous The ethylene content is within the range of 57-80%, it is within the range of 58-73% It is preferably 62 to 71%, more preferably 65 to 70%. Most preferably.

Preferred ethylene-α-olefin copolymers contain 62-71% molar ethylene. Ethylene content and number average molecular weight ranging from 60.000 to 120.000 - propylene copolymers, particularly preferred copolymers contain 62 to 71% ethylene. Ren content and ao, oo.

It is an ethylene-propylene copolymer with a molecular weight of ~too, ooo.

Copolymers can be produced using methods known in the art, e.g. using Ziegler-type catalysts. It can be prepared by any of the following methods. The polymer should be substantially amorphous.

After all, highly crystalline polymers are relatively insoluble in fuel oil at low temperatures; It is.

Additionally, the additive composition advantageously has a viscosity of at most 750 0, advantageously from 1,000 to 6,000, preferably from 2.000 to 5.0. ooo's further comprising an ethylene-alpha-olefin copolymer having a number average molecular weight. It's okay. Suitable α-olefins are as indicated above, or styrene and again propylene is preferred. Ethylene content is 60-77 mol% Advantageously, for ethylene-propylene copolymer, 86% by weight Up to mol % ethylene can be advantageously used.

Examples of hydrocarbon polymers are described in WO-A-9111488.

(v) Sulfur carboxy compound An example is given in European Patent Application No. 0.261.957, which is generally describes the use of compounds of formula.

(In the formula, -Y-R" is sO2""'NR'3R', -5o)'-'"'HR'lR" , -503'-"°'H1NR' R", -5o3'-'"'H3NR", - sowNR’R” or -So,R”, and -X-R”1t-Y-R” L< is -CONR' R", -Cot'-'"'NR31R", -Cot '-' l+1HNR' + R", -R'-COOR", -NR' COR '3, -R'　OR'', -R'　0COR13, -R', R13, -N　(C OR">R+' or Z'-' "'NR35R", -21-1 is SO3 '-' or -co, ``, and R'1 and R'' are at least 10 in the main chain. an alkylsialkyl or polyalkoxyalkyl containing carbon atoms; R' is hydrocarbyl, and each R1 may be the same or different. may be present, the stress R4 may be absent, and i; icl-Cs alkylene, Ct) may be a substituted hydrocarbyl group (this Ct ethylenic performance saturation Multi-component additive systems may also be used, with the ratio of additives used depending on the It will depend on the fuel used.

concentrate The concentrates of the present invention serve as a means for incorporating additives into neat oils such as distillate fuels. Conveniently, the incorporation may be carried out by methods known in the art. Also, dark The thick material may contain other additives if necessary, preferably in solution or liquid. 3 to 75% by weight, more preferably 3 to 601% by weight in a carrier liquid as a medium , most preferably 10-50% by weight of additives. carrier liquid Examples of hydrocarbon solvents, e.g. petroleum distillates, e.g. naphtha, kerosene, diesel oils and heating oils; aromatic hydrocarbons, e.g. aromatic fractions, e.g. Aromatic fractions sold as “Tsurupets”; and paraffinic hydrocarbons , for example, organic solvents including hexane and pentane. Of course, the carrier liquid , the additive and its compatibility with the oil need to be selected.

The additives of the present invention may be added to the net oil by other methods as known in the art. May be contaminated. If co-solvents are required, they may be combined at the same time as the additives of the invention. or mixed into the net oil at different times.

The additives of the present invention are compatible with the presence of various other additives commonly used in fuel compositions. Can be used below. Examples of such other additives are rust inhibitors, pigments, detergents, and emulsifiers. Disintegrants, dispersants, antioxidants, antistatic agents, metal deactivators, cetane improvers and smoke prevention agents Antismoke agents. Other additives such as is about 0. It may be present in an amount of 0.001 to 5% by weight.

Example The invention is particularly illustrated by the following examples only.

Additive The following additives were used.

Ethylene-vinyl acetate copolymer (additives A-E and Ni-S) code content medium % of content % of content (mol%) (weight%) (mol%) (weight%) ( mol %) Thus, additives A and B comprise a single copolymer, whereas additives C, D and E contain two types of copolymers.

Additionally, the following additives, each in the form of a single ethylene-vinyl acetate copolymer, were used: did.

Additive code Average vinyl acetate content The following materials were used as co-additives.

Polar nitrogen compound (additive F) Half amide/ 2-K,N'-dialkylamine, which is a reaction product that produced a half amine salt N,N-dialkylammonium salt comb polymer of do-benzoate (additives G) The monomer (the monomer has 16 containing a linear alkyl group of carbon atoms). Itaco with a number average molecular weight of approximately 4000 as measured by perchromatography (GP) nate polymer Comb polymer (additive H) Same as Additive G except that the monomer contains a linear alkyl group of 18 carbon atoms. polymer (Additive I) Fumaric acid is added to primary n-C++ alcohols and n-C++ alcohols as well as small amounts of By reacting with commercially available alcohols containing 2-methyl analogs of these alcohols, of about 9500, obtained by polymerization with vinyl acetate in a molar ratio of l:l. Copolymers of dialkyl fumarates with Mn Comb polymer (additive J) Fumaric acid was reacted with n-C1* alcohol and then vinyl acetate was added in a molar ratio of l:l. Dialkyl carbon having Mn of about 15,000 obtained by copolymerizing with malate copolymer fuel The following fuels with the indicated properties were used.

Code % wax (wt/wt) CP (cloud point) D-86 distillation (℃) ( )('C) IBP20% 50% 90% FBP at 10℃ below CP l 2.4 -4 140 208 250 334 3602 1.1 6 187 224 271 370 3923 2.2 -8 138 202 238 327 366 Note: IBP is the initial boiling point.

FBP is the final boiling point.

X% is the temperature at which X% by volume of fuel is distilled.

test The additive is dissolved in the fuel and the following tests are performed on the untreated fuel and on the fuel treated with the additive. Some of the additives are the additives of the present invention; Not additives, ie they were used for comparison.

(a) Cold Filter Plugging Point (CFPP) test “Journal of 　the In5titut　of　Petroleum'', Volume 52, 510 Issue, June 1966.

The procedure was performed as detailed on pages 173-285. This test is an automotive designed to correlate with the cold flow properties of middle distillate fuel oils in diesel engines. It is. Lower CFPP values were superior to higher values in the respective tables of test results below. Demonstrate performance.

(b) Extended Program Cooling Test (XPCT) The test is a test in which the wax in the fuel warms up. to indicate whether or not it passes through filters such as those found in chamber oil distribution systems. This is a designed slow cooling test.

In this test, the cold flow properties of the described fuel with additives were determined as follows: It was measured by 300 ml of fuel was linearly cooled to the test temperature at 2°C/hour, and then (The temperature was kept constant in Step 1. Gently stir the wax that had settled in the bottle.) and then cold filter plugging point (CFPP) filter collection. (This is the Journal of the In5 posture of P etroleum”, Volume 52, No. 510, June 1966, 173-285 (described in detail on the page) was inserted. Evening: Open the knob and get 500■ of mercury Empty was applied and 200ml of fuel passed through the filter and entered the graduated receiver. closed at the time. If 200ml passes the specified mesh size, it will be recorded as passing. However, if the filter became clogged, it was recorded as a failure.

LTFT (AMS 100.65) and film, both of which are between 30 and 40 μm. Volkswagen tank filter (part number KA/4-270/65.431 -201-511) with different sized filter screens. Using a CFPP filter assembly, measure the smallest mesh that fuel will pass through. did. The filter screen sizes are arranged in order of increasing size, i.e. The tests were as follows in order of decreasing severity: lOμ, 15μ , 20μ, 25μ, 500, LTFT, 350, ff, 250.200 .

1505120.100.80.60.40 and 30 (in this case, the numerical value alone is (indicates tush size). To aid comparison, the results in each table are evaluated in numerical order. and in this case lower numbers indicate better results than higher numbers.

result The results are shown in the table below, where the additive is represented by the additive code above. . EVA means ethylene-vinyl acetate copolymer by additive code, VA means vinyl acetate.

Examples marked "comp" are comparative examples.

Fuel l; Processing ratio EVA: 200pp+n; F: 200ppm; Ga1l 200ppln when not containing, 1100pp when containing H; H: 100pp+ n test EvA; mol% Auxiliary additive CFPP (℃) XPCT example VA (Lethe (Ing No.) Base -3,530# 1 (comp) A +5.5 F, G -7,5500 # (2) 2 (comp ) CI2.4 F, G -9LTPT (3) I D9.7 F, G -13, 510μ (1) 2 E 7.1 F, G -10,5ff (4) 3 (comp) A +5.5 F, G, H-9500 # (4) 4 (comp) CI2.4 F, G, H-1o 25 μ(3) 3 0 9.7 F, G, II -15,5 15μ(2)4E7. IP, G, H-18,010μ (1) Table 2 Fuel 3: Processing ratio EVA: 60ppm; F: 40ppm; l: 1100pp test EvA; mol% Auxiliary additive CFPP (℃) XPCT7 (co+np) K 16.6 -10.5 40# (7) 8 (comp) L 11.1 -1 3 80# (1) 10 N 8.5 -15 806 (1) 11 07.7 - 14.5 80# (1) 9 (camp) Q 4.8 -12.5 80# (1 )10(comp) R3,8-12,560:t(5)■! scolding country------ --Even Σ---- Murosaku Ichiichi table 3 Fuel 2; Processing ratio EVA: 60ppm; F: 40ppm test EVA; %le X CFPP ('C) XPCT12 (comp) K 16 ．． 6 -4.5 200# (6) 13 (comp) L 11.1 -3 20 0#(6)12M 10.2-4 350#(4)13N8.5-4. 5 LTPT (3) 14 07.7 -5.5 25μ (2) 15 P6.5 -4.5 350# (4) 14 (cornp) R3,8-2,520μ (1) Table 4 Fuel 2: Processing ratio F! VA: 60ppwh: F: 40ppva: J: 100 ppra exam EVA: Mol% CFPP (℃) XPCT15 (comp) K 16. 6 -4.5 200# (6) 16 (comp) L 11.1 -15 20 0# (6) 16 M 10.2 -17 500# (1) 17 N8.5 -1 8 350 # (3) 18 07.7 -18.5 500 # (1) 19 P6. 5 -16 350 # (3) + 7 (comp) 9 3.8 -17.5 35 0#(3) “Base” examples also refer to the fuel itself (i.e., without additives). It is.

1~! The example marked 9 is an example of the present invention and has improved performance over the corresponding comparative example. shows.

Continuation of front page (51) Int, C1,6 identification code Internal reference number C10M 145:14 (72) Inventor David Davis Brian William United Kingdom Oxford Dosha OEX 119 Bday Blueberry London Road Pound fur long (no house number) (72) Inventor Goverdan Danesh Gorton UK Oxford Code OEX 26 Davey King Street Guy Court 22 (72) Inventor Moa Ian England, Oxfordshire, Oex 143 Neat Arpin Gudong Lee Avenue 15

Claims (16)

[Claims] 1. Ethylene and unsaturated monomers with general formulas▲Mathematical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R6 is hydrogen or methyl, R5 is -○○CR1 group (In the formula, R5 is Hydrogen formate or C1-C26, more usually C1-C17, preferably C1-C6 is a straight-chain or branched alkyl group), or R5 is a -COOR1 group (of the formula where R5 is as defined above but is not hydrogen) and R7 is hydrogen or one -COOR group as defined above, and (i) more than one copolymer is If present, the arithmetic mean content of said unsaturated monomers in the copolymer is 11 mol. % or less, or (ii) if one copolymer is present, in the copolymer The content of said unsaturated monomer is in the range of 6.5 to 10 mol%) Additives containing oil-soluble copolymers. 2. Claim 1 comprising a copolymer in the range 7-10 mol%. Additives listed. 3. Additive according to claim 2, which ranges from 8 to 10 mol%. 4. Claim 1 comprising more than one copolymer in the range 5-10 mol% Additives listed in section. 5. Additive according to claim 4, in the range 6-10 mol%. 6. One or more aids for improving the cold flow properties of crude oil, lubricating oil or fuel oil The additive according to any one of claims 1 to 5 in combination with an additive. 7. One or more oil-soluble co-additives may include polar nitrogen compounds, comb polymers, polyoxygen selected from sialkylene compounds, hydrocarbon polymers, and sulfur carboxy compounds. The additive according to claim 6. 8. The co-additive comprises at least 1 molar ratio of a hydrocarbyl-substituted amine. Reaction with a hydrocarbylic acid having 1 to 4 carboxylic acid groups or its acid anhydride Polar compounds containing amine salts and/or amides produced by The additive according to claim 7, which is a nitrogen compound. 9. Claims wherein the unsaturated monomer is vinyl acetate or vinyl propionate. The additive according to any one of items 1 to 8. 10. A large proportion of crude oil, lubricating oil or fuel oil and a small proportion of claims 1 to 9 A composition comprising a mixture with an additive according to any of paragraphs. 11. Addition in a total proportion of 50-500 ppm (by weight) based on the weight of the oil A composition according to claim 10, including auxiliary additives, if present. thing. 12. The composition according to claim 10 or 11, wherein the oil is a middle distillate fuel oil. A product. 13. Any one of claims 1 to 9 in an oil or an oil-miscible solvent. Additive concentrates containing the listed additives. 14. Claims 1 to 9 for improving the low-temperature properties of oil. Use of additives listed above. 15. 15. Use according to claim 14, wherein the oil is a fuel oil. 16. Use according to claim 15, wherein the fuel oil is a middle distillate fuel oil.